Copolymer of diallyl phthalate and unsaturated alkyd resin



Patented June 22, 1948 UNITED STATE PATENT OFFICE COPOLYMER 0F DIALLYL PHTHALATE AND UNSATURATED ALKYD RESIN Edward L. Kropa, Old

Greenwich, Conn, assignor to American Cyanamid Company, New York, N. Y., a corporation of No Drawing. Application July 12. 1943, Serial No. 494,348

mixture, as well as to improve the properties and characteristics of resulting gels.

Another object of this invention is to prepare compounds particularly suitable for use as coating composition and as components in coating compositions.

A further object of the present invention is to prepare molding compositions and especially to prepare clear and colorless molded materials. Another object of this invention to is prepare laminated moldings having high strength and I other desirable properties.

A still further object of this invention is to provide molding compositions suitable for injection molding. Other objects will be apparent from the description.

Substantially insoluble, substantially infusible resins may be prepared by means of the chemical reaction or polymerization of a mixture containing a resin possessing a plurality of polymerizably reactive alpha, beta enal groups (i. e.,

C=$( =O) and an organic substance which contains the polymerizably reactive group CHa=CHCH2-. The high boiling allyl compounds are the preferred reactive organic substances. Such mixtures may be utilized in coating compositions, in molding compositions, in laminating, in adhesives,

' in casting compositions, etc.

For the sake of brevity the organic substances which contain the polymerizably reactive group,

CH2=C will be referred to herein as."reac-- tive materia or as reactive materials containing the CH2==C group" and they are thus to be distinguished from the resins which possess a plurality of polymerizably reactive alpha, beta enal groups which are designated herein as "reactive resins or as unsaturated alkyd resins.

Many of the reactive materials containing the CH2=C group are'solvents and therefore the reactive resins may be dissolved therein to form liquid compositions which may be used as such without the addition of any other solvent unless particularly desirable. It is to be understood, however, that I am not restricted to liquid substances which actually act as solvents since in some cases the organic liquid substance may in fact act as a solute rather than as a solvent, it being dissolved by the resin, or a colloidal solution may be produced instead 01 a true solution. Furthermore, the reactive material may be a resin containing a plurality of CH2=C groups or CH2=CHCH.2- groupsf Such'a substance could be cured by a reactive resin or by a go reactive substance which contains polymerizably 26 Among the reactive resins used in this inventionfor interaction with the reactive reactive alpha, beta enal groups. Such sub- .stances may be derived from alpha, beta unsat urated organic acids, for example, by esterification of such acids. the practice of material containing the CH2=C group are those which are derived from alpha, beta unsaturated organic acids and, therefore, contain the reactive groupings present in these acids. The term acids as used herein is intended to include the anhydrides as well as the acid themselves since the former may be used instead of the acid. The term alpha, beta-unsaturated organic acid as used in the art does not include acids wherein the unsaturated group is part of an aromaticacting radical, as for example, phthalic acid, and the same definition is adopted herein.

The resins are preferably producedby the esteriflcation of an alpha, beta-unsaturated polycar- I boxylic acid with a polyhydric alcohol and particularly a glycol. Although esterification of the acid with a polyhydric alcohol is perhaps one of the simplest, most convenient ways of obtainin a reactive resin, I am not precluded from using resins otherwise derived from alpha, betaunsaturated organic acids. Reactive resins suitable for my invention are any of those containing a plurality of polymerizably reactive alpha, beta enal groups.

Pmm'rron or m Poanuuzm: Minoan A reactive resin such as those prepared by the \esteriilcation of alpha, beta-unsaturated organic acids and a glycol or other polyhydrlc alcohol as oi the reactive group CH2=C and none of them contain conjugated carbon-to-carbon double bonds. Compounds containing a conjugated system of carbon-to-carbon double bonds are known to react with themselves or with other unsaturated compounds such as the maleic esters, by a 1,24,4' addition mechanism such as that which has become generally known as the Diels-Alder reaction. n the other hand, compounds such as those used according to the present invention and which contain no conjugated carbon-tocarbon double bonds obviously cannot undergo this type of reaction with the maleic esters. Accordingly, my invention is not directed to the use oi unsaturated compounds containing conjugated systems of carbon-to-carbon double bonds. Many substances which contain a carbonto-carbon double bond conjugated with respect to oxygen are suitable for use according to my invention since they do not react with unsaturated alkyd resins in an undesirable manner, but, instead, copolymerize or interpolymerize to form substantially intusible, substantially insoluble resins.

The reactive allyl compounds which may be used are any of those compounds which contain the CH: =CHCH2 group and which do not have a boiling point below about 60 0. Of the allyl compounds which may be used the allyl' esters form a large class all of which are suitrides.

able. The reactive ally] compounds which have phthalate and diallyl succinate. Other allyl compounds may also be used which are not necessarily high boiling. As pointed out in my copending application, Serial No. 487,034, filed May 14, 1943, substantially insoluble and substantially ini'usible resins may begprepared by reacting or polymerizing any of the dollowing with a polymerizably reactive resin of the type described herein, i. e., unsaturated alkyd resins containing a plurality of alpha, beta enal groups: allyl aicohol, methallyl alcohol, allyl acetate, allyl lactate, the allyl ester oi alpha-hydroxyisobutyric acid, allyi acrylate, allyl methacrylate, diallyl carbonate, diallyl malonate, diallyl oxalate, diallyl succinate, diallyl gluconate, diallyl methylgluconate, diallyl adipate, the diallyl ester of azelaic acid, diallyl sebacate, diallyl tartronate, diallyl tartrate, diallyl silicone, diallyl silicate, diallyl fumarate, diallyl maleate, diallyl mesaconate, diallyl citraconate, diallyl glutaconate, the diallyl ester or muconic acid, diallyl itaconate, diallyl phthalate, the diallyl ester of endomethylcue tetrahydrophthallc anhydride, triallyl tricarbailylate, triallyl aconitate, triallyl citrate, triallyl phosphate, trimethallyl phosphate, the

-diallylester of glycol dicarbonate (i. e.,

the diallyl ester oi ethylene glycol dimalonate, the diallyl ester of ethylene glycol dioxalate, the diallyl ester of diethylene glycol dicarbonate, the

diallyl ester 01' diethylene glycol dimalonate, the

diallyl ester of dlethylene glycol dioxalate, the diallyl ester of carbonic acid or oi other dlcarboxyllc acid, dlesters 01' other glycols, e. g.,

propylene glycol. the butylene glycols, triethylene glycol, etc., tetraallyl silicate and other tetraallyl esters. Tetraallyl compounds are not easily prepared by direct esteriflcation. One way for preparing such compounds is by the use of the acid chlo- Other 'allyl compounds which may be used for reaction with a polymerizable and unsaturated alkyd resin include reaction products of allyl malonate with iormaldehyde or glyoxal, such compounds having the following formula respectively:

CHr=CHCHz-0OC 0O0CH:CH=CH:

cH-cm-on oH,=cn-oH,-0oo ooocni-cnpcni CHFCH-CHr-OOC coocm-on=cm C=CHCE= cn==oH-omo0 00CH:-CH=CH1 Another compound which may be employed is the tetraallyl 'ester obtained by the reaction of allyl malonate with chloroform in the presence of sodium allylate and which has the following formula:

sun another compound which may be employed is the compound having the following formula:

and it may be preparedjby reacting allyi acetyi ene dicarboxylate with allyl malonate.

The polymerization catalysts organic superoxides, aldehydic and acidic perox ides. Among't e preferred catalysts there are: the acidic per xides, e. g., benzoyl peroxide, phthalic peroxide, succinic peroxide and benzoyi acetic peroxide; fatty voil acid peroxides, e. g.. coconut oil acid peroxides, lauric peroxide, stearic peroxide and oleic peroxidei alcohol peroxides, e.-g., tertiary butyl hydroperoxide usually called tertiary butyl peroxide and terpene oxides, e. g., ascaridole. Still other polymerization catalysts might be used in some instances such as soluble cobalt salts (particularly the linoleate and naphthenate), p-toluene sulfonic acid, aluminum chloride, stannic chloride and boron trifiuoricle.

The term polymerization catalyst as used in this specification is not intended to cover oxygen contain-ed in the resin as an impurity. While this small amount of oxygen would only catalyze the reaction tota very smallextent, in order to eliminate any ambiguity the term polymerization catalyst is specifically defined as excluding any include the 1 trol conditions:

oxygen present as an impurity in the resin itself.

The concentration of catalyst employed is usually small, 1. e., for the preferred catalysts,

irom about 1 part catalyst per thousand parts heat, light, or a combination of both. Ultraviolet light is more effective than ordinary light. The temperature of conversion depends somewhat on the boiling point of the reactive material and also on the pressures used. At atmospheric pressure, as in coating and casting operations, temperatures near or above the boiling point are unsuitable in most instances since substantial amounts of the reactive material would be lost by evaporation before the reaction between the resin and reactive material can be completed. Accordingly a temperature between room temperature (about 20-25 C.) and the boiling point is usually employed where polymerization of this nature is carried out. The rate of polymerization doubles for about each ten degrees (C.) rise in temperature for this reaction. A temperature is selected which will give a suitablereaction rate and yet not cause substantial volatilization. The following table shows the approximate polymerization temperatures most suitable for the named reactive materials:

Reactive Material Temperature liange fggggig diallyl maleate Room temp. to about 110 C. 50 to 90 C. diailyl phthalate. Room temp. to about 150 C. 50 to 90 0.

Obviously it will be necessary to use lower temperatures if large or very thick pieces are being cast because of the exothermic reaction and poor heat conductivity of the reacting mixture.

Where suitable precautions are taken to prevent evaporation of our reactive material or where pressure molding is used higher temperatures than those mentioned above could beused. Since the time of curing is desirably much shorter (in pressure molding at elevated temperatures) v and since the reactive material containing the CH2=C group would not be lost so easily, a higher temperature is preferred.

The particular reactive resin, reactive material and catalyst is selected according to the type of product desired, taking into account the solubili- Emample 1 Diethylene glycol maleate resin and diallyl maleate were mixed in various concentrations and treated with 0.4% of benzoyl peroxide. The

following results were obtained after curing four days at 58 C.

Diollyl Resin Mm Result Per cent Per cent 10 Q) Clear-sort. 30 70 Clear-semihard-gelled alter 24 hrs.

60 50 Do. 70 30 Do. Do.

Similar results are obtained substituting diallyl fumarate and diallyl phthalate.

Example 2 Ethylene glycol maleate resin (acid number 50) and diallyl'phthalate were mixed in various con centrations and treated with 0.4% benzoyl peroxide. The mixtures were heated at 44 C.-for twenty-four hours and then at 100 C. for three hours with the following results:

a 1 Results Y Phthelaie 24 hours 27 hours Per cent Per cent 0 100 Liquid Liquid.

i0 00 Slightly opaque gel. Slightly opaque gel.

do Do.

60 Clear gel Example 3 Similar results were obtained with diethylene glycol maleate resin (acid number 32) and ethylene glycol maleate resin (acid number reacted with other diallyl esters:

Results Parts Parts a Resin 0! Solvent of B01- $32;

Resin vent o Ethylene glycol 10 Dlallyl succinate.. 3. 3 Clear gel.

maleate.

Do 10 .do 10.0 Clear gelblue. Do 10 ..do 15.0 Do. Diethylene glyl0 Diallyl phthelate.. 3.3 Clear gel.

c maleate.

10 ..do 10.0 Do. 10 Diallyl succinate 3. 3 Do. 10 .do 10.0 Do.

Diallyl sebacate was foundnot to be appreciably soluble in ethylene glycol vor diethylene glycol maleate resins but was soluble in long-chain glycol resins such. as, for example, decamethylene glycol maleate resin.

Example 4 Ethylene glycol maleate resin (13 parts) was mixed with allyl alcohol (7 parts) "and 0.2%

benzoyl peroxide. At C. the mass gelled in eight to ten minutes.

' Example 5 Example 6 Approximately 250 parts of diallyl maleate were heated in a bath. The temperatures of the bath as well as the solution were recorded.

amass I 7 8 diallyl ester. 0.05 part of cobalt naphthenate in Tern Tm m toluol and 0.2 part of benzoyl peroxide in di agi as 'o. The following results were obtained:-

u m I Triothylonc ResuitatU'O. al3 it. 1% L 55"? 33 1: lg 11 min. co mm. 14: 14s Pom Pom Port:

60 0 40 D112. As soon as the exothermic reaction was ap- :3 =3 3 2; preached the material was removed from further contact with heat for approximately fifteen 'b 1o minutes and then further heated. The mass was then allowed to stand at room temperature and then distilled in vacuo. Approximately 60 parts of colorless viscous resin was obtained after the monomeric diallyl maleate had been removed.

2 parts of the resinous diallyl maleate were dissolved in 1 part of ethyl tumarate and treated with 0.2% of benzoyl peroxide. In approximately ten minutes at 90 C. a cloudy hard resin resulted. A

The resinous diallyl maleate was mixed with equal parts 01' ethylene glycol maleate and treated with 0.5% of benzoyl peroxide. At 50 C. curing resulted in a hard clear resinous mass.

Other resinous substances containing a plurality of unsaturated groups such as allyi cellulose, methallyl cellulose, crotyl cellulose, etc. could be treated in a similar manner with reactive materials or with reactive resins.

Example 7 500 parts of phthalic anhydride, 103 parts of ethylene glycol. 225 parts of allyl alcohol, 225 parts of toluene and 3.4 parts of p-toiuene suifonic acid were heated in such a manner that the hot vapors passed through a bubble-cap fractionating column before condensing. The water was separated and the other components returned to the still. The heating was continued for approximately sixteen hours. The mass was then heated in a low vacuum to remove the low boiling constitutents and then in a higher vacuum (4 mm.) The bath around the flash was maintained at approximately 180 C. for 2.5 hours to remove volatile materials.

The residue remaining was a soft iiuid viscous resin of acid number of 38.

One part of the above resin was mixed hot with 1 part of alpha-propylene glycol maleate resin and treated with 0.2 part of benzoyl peroxide. At 120 C. rapid curing was obtained.

Example 8 Example 9 A resin formed by the reaction of 1 moi of triethylene glycol with 1 moi of a mixture containing fumaric acid and phthalic anhydride (75%)- was mixed with ethylene glycol maleate resin in various proportions. 60 parts of these mixed resins were mixed with 40 parts of a Compositions similar to those of Example 9 were made using the same proportions of diallyl maleate resin and catalyst. The following results at 90 C. were obtained with the resins indicated,

n the proportions being given in moi tain a certain number of oxygen Resin 60%hflg}ethy]6H6 glycol, 12.6% Fumaric, 37.5% Miriam o. 'iriethylene glycol, 25% Furnaric, 257 Phthallc. o 'Iriethylene glycol 40% Fumaric, l6 0 Phthalic o Triethyicnc glycol, 25% Fumaric, 25% Fineneumaric (Made by reacting 95 moi of pinene to 1 moi of fumaric) Example 11 60 parts dlallyl maleate were mixed with 40 parts of diethylene glycol phthalic-maleic resin phthalic-50% maleic). Films of this mix-- ture dried from the bottom but the top remained soft. The addition of linseed iatty acids to the good surface drying.

Example 12 Phthalic anhydride (150 parts), triethylene glycol i160 parts) and linseed oil (15 parts) were heated in an atmosphere of CO2 at 180 C. for

eight hours, resulting in an acid number of 31.8.

.To the cooled mix there was added malelc andrier and 0.1% of mercaptobenzothiozole were 7 Example 14 46 parts of glycerol, 49 parts of maleic anhymymg time They were hard and dride, 35 parts of linseed oil acids and 69 parts of undecylenic acid were heated to 180 C. during about three hours. Compatibility did not occur and the mass gelled. Upon the slow addition of the linseed oil acids to the hot mixture of the other ingredients compatibility was established.

The resin (12 parts) resulting from this reactionwas dissolved separately in diallyl maleate (8- parts) and also in toluene (8 parts) and treated Example 15 V Y A resin was prepared by the esteriflcation of 2 .mols of diethylene glycol, 1 mol of maleic anhydride, 1 moi of phthaiic anhydride', (of the total of the foregoing-ingredients) of linseed oil acids and glycerine in an amount equivalent to the linseed fatty acids. A mixture of 60 parts of resin and 40 parts of diallyi maleate was treated with 0.05% cobalt naphthenate.

, Another solution was also made up of the following composition:

' Per cent Nitrocellulose Q.-. 29.2 Ethanol 12.5 Ethyl acetate 58.3

One part of each of the above solutions was mixed with one part of toluene and the mixture applied to tin. The film was baked for fortyilve minutes at 90 C. to yield a clear. glossy, hard film.

The following examples show molding compositions and shaped or molded articles comprising my polymerizable reactive mixtures:

Example 16 To 125 parts of cellulose filler (Novacel) about 22 parts of diallyi phthalate containing about 0.1-0.2 part of benzoyl peroxide are added and the resulting composition is placed in a suitable mixer, e. g., a Banbury mixer. and agitated until homogenized. About '45 parts of the solution containing 75% of ethylene glycol maleate and 25% of diallyl phthalate are added and the entire mixture is ground for about 35 minutes.

The resulting product is molded at temperatures of about 130150 C. and at pressures up to about 3000 pounds per square inch. Small dishlike moldings are produced at this temperature and pressure in about 3 minutes.

This compositionmay be ground it necessary to disperse the benzoyl peroxide thoroughly. The mixture is molded in polished molds for about 3 minutes at about 130 Cland at approximately 200 pounds per square inch pressure. A clear, light-colored homogeneous molding is obtained. The pressure may be varied considerably and satisfactory moldings have been sures as low as 150 pounds per square inch at about -140 C. This composition is also suitable for injection molding and in this instance, the liquid composition describedabove isforced into a hot mold.

Example 18 I Par Resin "E" 60 Diallyl phthalate 40 Benaoyi peroxide 0.5

Resin E is dissolved in the diallyl phthalate and the benzoyl peroxide is added. The above- -solution is coated onto glass fabric "and placed between smooth platens. 'A pressure of-a bout 10-15 pounds/sq. in. is apiplied to the platens. in

order to remove entrapped air. The assembly 'is then heated at about C for about 2 hours.

The platens are removed and a stiff sheet results. Using 2-plys of glass cloth, possessing the trade name EC-l1-161"(sold by Owens-Corning Fiberglas Corporation), the following physical properties were obtained using the above'resi'nous composition:

Tensile strength (+25 C.):

, 32,000 pounds/sq. in. 27,100 pounds/sq. in.

The difference in strength was-obtained by cutting specimens parallelto and at right angles to the warp. s

The modulus in bending values were:

. 9.6x 10 pounds/sq. in. at .-40 C. 6.1x 10 pounds/sq; in. at 40 C. 9.6x 10 pounds/sq. in. at +25 C. 7.3x 10 pounds/sq. in. at +25 C.

Here again tests were conducted parallel to and at right angles to the warp.

The abo'e liquid composition may be applied by means of a doctor blade, by dipping, followed by squeeze rolls, by spray or bybrush.

Resin -E" above was prepared by heating 6 mols of diethylene glycol, 5 mols of fumaric acid and 1 mol of sebacic acid at about 200 C. until an acid number ofabout 50 was obtained.

The above composition is cast between sheets of glass. A paper spacer of approximately 30 mils is used to separate the glass sheets. The resin is forced into this space by means of a hypodermic needle. The assembly is maintained for about 1 hour at 150 C. The assembly is cooled and placed in cold water. A thin, flexible hard sheet of resin resulted. The composition is especially transparent since both sides of the sheet had taken the surface from the glass. 3

Such sheets of resin may be used directly or may be sealed onto other surfaces and used as a coating. When such materials are to be used as coatings, it is preferable toabrade one surface. This may be accomplished mechanically or in the manufacture thereof by theuse-of etched glass as one castin surface inthe above assembly.

- Example 20 A thin flexible sheet may be prepared by using a formulation such as follows in the process outlined in Example 19.

made at pres- Parts RJBSiI'l F" 50 Diallyl phthalate 50 Benzoyl peroxide 1 Resin F" is prepared by heating 2 mols of sebacic acid, 1 mol fumaric acid and 3 mols of ethylene glycol at about 200 C. until the acid number is about 50.

A flexible sheet is stormed which is similar to that obtained in Example 19.

Example 21 In order to produce compound curved 1aminated forms, the following procedure has been found satisfactory: Canvas or glass cloth cut to size is impregnated with the reactive mixture employed in Example 18. The layers of impregnated resin are placed in an appropriate form and a. vacuum applied, suitably with a rubber bag. The assembly is then heated for approximately 5 hours at 110 C.

Example 22 Parts Diallyl phthalate 48 Ethylene glycol maleate resin 32 Toluene Ethanol 10 Benzoyl peroxide 0.6 t-Butyl peroxide 0.4

Canvas is impregnated with the above solution and the excess, if any, is removed by passing the impregated canvas through squeeze rolls.

The impregnated canvas is then 'placed in an oven at about 80 C. until the resin has been partially converted to the infusible, insoluble stage. This operation requires approximately 2-3 hours. The impregnatedcanvas should be molded immediately or if allowed to stand -for any time, precautions should be taken to avoid exposure to air or oxygen.

The sheets of impregnated canvas are cut, stacked and molded under heat and pressure at about 2000-3000 pounds per square inch and at temperatures around 125 C. for approximately 4 hours, thereby producing a laminated cloth plate of very high transverse strength.

Alternatively, cut canvas sheets may be impregnated with the above composition without the use of the volatile solvents, alcohol and toluene.

The solution of diallyl phthalate and alkyd resin is applied to canvas using equal weights of canvas and reactive composition. The assembled sheets are placed between platens and placed in a press. A pressure of about 50 pounds/sq. in. is applied and the mass cured at 150 C. for 1.5 hours. A stiff cured resinous material results. Paper may be impregnated in a similar manner. For example, a composition containing approximately 45-50% resin has a transverse strength of about 16,000-l9,000 pounds/sq. in. This lam- ;J'xinated plate is particularly suitable for use in production of gear wheels because of the high transverse strength and since it may be machined easily.

Example 23 Parts. Ethylene glyco1 maleate resin 60 Dlallyl maleate 40 Benzoyl peroxide 0.7 Cobalt naphthenate 0.04

This mixture is used to impregnate canvas and the impregnated canvas is heated at about 80 C. for around 30-35 minutes in an oven. T

12 material is then cut, stacked and molded at a pressure of about 2500-3000 pounds/sq. in. at a temperature of about 125 C. and for approxi- 'mately 3 hours. The molded plate thus produced has a transverse strength of about 17,000

' pounds/sq. in. and it contains about 40 per cent resin. The strength may be increased and the electrical properties may be improved somewhat by curing the resin at lower temperatures, e. g., C. and at ordinary atmospheric pressures. This, of course, requires a correspondingly longer time for the conversion to the infusible, insoluble stage.

Alternatively, the impregnated cloth may be immersed in an inert fluid for about 35 minutes at 80 C. to bring about partial curing. Examples of such inert fluids are: glycerol, mineral oil, etc.

Example 24 Parts Resin G 50 Diallyl maleate 50 Benzoyl peroxide '1 This composition is applied to paper on a tube rolling machine, the machine comprising suitable rollers for paper and a means for distributing a uniform coating of resin on the paper. After the resin-impregnated paper has been rolled,

the roll is cut, stacked and partially cured (i. e.,-

polymerized) at about C. and then molded at somewhat higher temperature, e. g., -130" C. at a pressure of about 2000 pounds/sq. in. The resulting molded plate has good electrical properties and it has excellent transverse strength. If desired, cylindrical moldings can be produced by suitable modification of the apparatus and process.

Resin G is prepared by heating at about 180 C. under an inert atmosphere 650 parts of phthalic anhydride, 420 parts of maleic anhydride, 800 parts of triethylene glycol, 410 parts of ethylene glycol and 180 parts of linseed oil fatty acids in a suitable reaction chamber provided with a reflux condenser which has a water trap to separate the water formed during the esterification from the condensate. The mixture is heated for about 4-12 hours or until a relatively low acid number is obtained, e. g., about 20.

VTSCOSITY ADJUSTMENT or REACTIVE Mix'rtmr.

It is sometimes desirable to reduce the viscosity of our mixtures of reactive resin and reactive material containing the CH2=C group, as, for instance, when a very viscous resin is to be used for coating. It is possible to do this by adding an esteriflcation catalyst, e. g., p-toluene sulfonic acid and then heating until the viscosity goes down. The mechanism of this change is probably reesterification. This is also useful when the composition is to be baked at high temperature, under which conditions the reactive material would be lost in part by evaporation. If this thinning process is carried out, the reactive material is combined with the resin by reesterification and is not lost. It is also desirable to add a polymerization inhibitor before. the heating or "thinning process.

Example 25 A resin made by esteriflcation at C. of 294 parts of maleic anhydride, 121 parts sebacic acid, 227 parts of ethylene glycol, 32 parts of linseed fatty acids and 3.6 parts of p-toluene suli'onlc acid was mixed with diallyl maleate in Q ratio Of 80 parts of resin and 40 parts of 13' diallyl maleate, 0.01% p-toluene sulfonic acid added. and the mixture heated in an oil bath at 90 C. for flve hours. The viscosity decreased from to 8 poises.

T In casting or molding operations using a mix ture of a reactive resin and reactive material containing the CHa=C group, it may sometimes be desirable to body the reactive mixture before adding the catalyst in order to cut down the induc tion period which would otherwise be too long. This may be done by heating a mixture of resin and reactive materialfrom about 70 C. to'about 110 0., preferably at about 90 C., for sufllcient length of time to substantially reduce the induction period. This time will vary with each resinreactive material combination with the initial viscosity and other such factors but may be determined by observation of the rise of viscosity. The heating should continue until the viscosity begins to rise rapidly. A general rule for determining the heating time is to heat the mixture until the viscosity is about two to three times the initial viscosity.

After the bodying operation is carried out, the polymerization catalyst is added. to the mixture and the whole subjected to polymerization conditions. The use of liquid peroxides instead of solid peroxides is an advantage after bodying the resin mixture since it is diflicult to get the solid peroxides dissolved rapidly enough. Peroxides of the coconut oil acids, tertiary butyl peroxide and ascaridole are suitable liquids.

By the use of this process the induction period is cut down from approximately /2 to A; the time that is required when the bodying process is not used. Even greater reductions are obtained with some mixtures.

In bodying reactive mixtures containing the reactive resin and a reactive material containing the CHz=C group wherein the proportion of reactive material is greater than about 30%, the viscosity rise is so sudden that it may be somewhat diflicult to control it. Accordingly, if it is desired to body a resin-reactive material mixture containing more than 30% of reactive material, an alternative procedure is used. By this method one first bodies a mixture containing only 30% of reactive material. Then a small portion of additional reactive material is added, for example, sufllcient to make the reactive material concentration 40% and then this is bodied. -If still more reactive material is desired, another small portion of reactive material is added and the bodying process repeated. This process is repeated until the desired concentration and viscosity is obtained.

ADDITION or Irtmsrrons One of. the difficulties in the use of the compositions described above is that they are not susceptible to storage in the mixed form because polymerization will usually take place even at room temperature within a comparatively short time. Moreover, when it is desired to cure of the-concentrations of inhibitor and catalyst, a uniform product is obtainable with a good reaction velocity. Upon subjection of this mixture to polymerization conditions such as heat, light or a combination of both,-and with or without pressure, an infusible, insoluble resin is produced which has many more desirable characteristics than the resins produced by the polymerization of mixtures not containing the polymerization The inhibitor may be incorporated in the reactive resin-reactive material combination (either before or after bodying) or it may be added to the original reactive resin before or during the esterification of the said reactive resin. By adding the inhibitor before the csteriflcation it is sometimes possible to use an inhibitor which would otherwise be substantially insoluble in the reactive resin-reactive material composition. By adding the inhibitor to the unesterified mixture the inhibitor may become bound into the resin upon subsequent esterification.

Example 26 Resins were made up of the following compositions by esterification for the same length of time at 0.:

' Resin No. 1 I Resin No. 2

Ingredients Maleic Anh dride 49 49 Ethylene G ycol- 4i 4! Benzaldehyde Rmc'rrvn Rssms AND THEIR PREPARATION Reactive resins suitable for polymerization with reactive materials containing the CH2=C group in accordance with the teachings of our invention are those which contain a plurality of alpha, beta enal groups- The simplest members .of this group are those produced by the esterification of an alpha, beta-unsaturated organic acid with a polyhydric alcohol.

The preferred polyhydric alcohols are those which contain only primary hydroxyl groups since the presence of secondary hydroxyl groups may make it diificult to obtain rapid esterification. The glycols are generally preferable. If colorless resins be desired or if optimum electrical properties be desired, it is preferable to use glycols l which do not have any oxygen bridges in their structure since the presence of oxygen linkages may lead to the formation of color bodies during the preparation of the resin, By the use of glycols which do not contain the oxygen bridges clear colorless resins may be produced. On the other hand, oxygen bridges may be desirable if the resin is to be used in coating as they cause iilms. to dry faster.

The particular choice of glycol or other polyhydric alcohol, used in preparing the resin is governed mainly by the physical properties desired oi the intermediate and ilnal polymerization products, especially hardness, impact resistance, distensibility, refractive index. adhesion, compatibility relationships, etc. including also solvent,'.water alkali, acid or chemical resistance in general;

, The alpha, beta unsaturated organic acids which I prefer to use in preparing the reactive resins include maleic, Iumaric, itaconic and citraconic. although other similar acids could be substituted such as mesaconic acid, aconitic acid andhalogenated maleic acids such as chlormaleic acid and any of the foregoing could be substituted in part with acrylic, beta bcnzoyl acrylic inethacryiic, M-cyciohexene carboxylic, cinnamic,

and crotonic acids. Obviously, various mixtures of these acids can be used where expedient.

The -reactive resins may be modified with other substances which are used in alkyd resins, i. e., monohydric alcohols, monobasic acids or dibasic proportionoi' a polymerizably active dibasic acid.

e. g., maleic, in the reactive resin, a hard, tough polymer is produced upon subsequent reaction of said reactive resin with a reactive material containing the CH2=C group. On the other hand, if the reactive vresin is obtained from a .relatively small proportion of polymerizably accordance with my invention are preferably those having an acid number not greaterthan' 50 although in some cases resins having an acid numher as high as 100 may be desirable. Generally,

acids, e. g, piithalic acid, succinic acid, glutaric acid, 'adipic acid, azelaie acid, sebacic acid, etc., which do not contain groups nolymerizably reactive with respect to organic substances containing CH2==C groups. These modifying agents are usually used as diiuents or plasticizers, chemically combined in the resin. The use of a small proportion of the saturated dibasic acids generally improves the mechanical properties of the resins after copolynierizatlon with the materiai containing the GH2=C group.

The reactive resins may be prepared from polyhydric alcohols other than the glycols or from the acid number should be as low as possible, but this is sometimes controlled by practical considerations of operation such as time, temperature and economy.

The resins should be so formulated that the carboxyl groups of the acids are reacted with the theoretical molal equivalent of the hydroxyl groups of the alcohols. In this connection it is to be noted that the hydroxyl groups of modifying alcohols as well as the carboxyl groups or modifying acids should be included with the hymixtures including a glycol and a higher poly-.

cation of an unsaturated alcohol containing a;

C%=C group. Examples of such, alcohols are ally! alcohol and methallyl alcohol.

While the reactive resins may be modified in the same general manner as other alkyd resins, it is preferable to have at least polyhydric alcohol in the reactive mixture and at least polybasic acid in said reactive mixture. If -a inonohydric alcohol or a dibasic acid which does not contain polymerizably active groups with respect to organic substances containing the cr1==c groups be used, the proportion of such substances will depend on the properties required of the polymerized reactive material-reactive resin mixture. By the use oi a relatively large Exampies of these are glycerol,

Kill

droxyl groups and carbonyl groups of the principal reactants, the polyhydric alcohol and the alpha, beta unsaturated polycarboxylic acid, respectively. v

If it be desirable to introduce lower alkyl groups into the resin, this may be done by using malelc esters of monohydric alcohols, e. g., ethyl maleate. The alkyl ester will then be united with the resin by polymerization. This could not be accomplished with the saturated type of alkyd, e. g., phthalic acid esters of polyhydric alcohols.

Resins which contain a plurality of alpha, beta enal groups are sensitive to light, heat and polymerizing catalysts. Since oxygen'tends to cause these resins to polymerize, it is desirable that the resins should be made in the absence of this substance, especially when colorless resins are required. The exclusion of oxygen and polymerizing catalysts is desirable during the preparation of the resin and the presence of dissolved oxygen in the original reactants is also preferably avoided. Moreover, dust and extraneous particles that reagents may pick up usually should be removed, especiallyif colorless resins.

are desired. One manner in which the dissolved gases and other extraneous impurities may be removed is through the distillation of the ingredients into the reaction chamber in the absence of air.

in order to keep oxygen from, contact with the reactants an inert gas such as-carbon dioxide or nitrogen may be introduced into the reaction chamber. This may be.done either by merely passing the gas over the surface or by bubbling the gas through the liquid reactants. In the latter instance it may be made to perform the added function of agitating the mixture thus eliminating the necessity for mechanical agitation. The inert gas will also carry away at least part of the water formed and toward the end of the reaction it can be used to carry away the reactants still remaining unreacted. Upon separation of thewater vapor the used carbon dioxide or other-inert gas would be particularly suitable for making high grade colorless resins since 'any residual reactive impurities suchas oxygen would have been removed in its passage through the first batch of resin reactants.

The effect of light. is not so important if the reactants are purified and the reaction carried on in an inert atmosphere as outlined above. However, as an added precaution the esteriflcation may be conducted in the dark. It is also advisable to avoid local overheating and discoloration is minimized if the reaction is conducted below a temperature of about 200 C. To avoid overheating it is advisable to raise the temperature slowly at the beginning, especially if an anhydride be used since the reaction between an anhydride and an alcohol is exothermic. 4

The preparation of the reactive resins is illustrated in the following examples, the reactants being given in parts by weight.

PREPARATION or RESIN "A" 98 parts of freshly distilled maleic anhydride were reacted with about in excessof equimolecular proportions of freshly distilled ethylene glycol (68 parts) at about 170-175 C. An excess of ethylene glycol is preferred because of its high volatility. The mixture is continuously agitated and carbon dioxide is introduced into the reaction chamber during the reaction thereby blanketing the surface of the reactants. After eight to twelve hours a clear, water-white resin is produced with an acid number of 35-50.

PREPARATION or RESIN B Diethylene glycol (106 parts) and maleic anhydride (98 parts) were separately vacuum dis=- tilled into a reaction chamber which had been used in previous preparations, and the mixture was stirred mechanically while carbon dioxide gas was introduced over the surface of the resin to exclude air and to remove water that was formed in the esterification. The reaction was conducted at 170 C. for a period of from eight to twelve hours yielding a resin of acid number of 35-50.

PREPARATION or REsIN C 1200 parts of maleic anhydride were mixed with 1023 parts of alpha propylene glycol (equivalent to one mol of each plus approximately 10% of the glycol). This mixture was heated with agitation in an inert atmosphere at 150-165 C. After about four hours the resin turned opaque on cooling. After about eleven hours heating a resin is obtained which is somewhat brittle at room temperature and the acid number is between 35-50.

PREPARATION or REACTIVE RESIN AZEOTROPICALLY Since the viscosity of the resin frequently becomes quite high if the -esterificatiori is carried to a low acid number, it may be desirable to produce the resin under azeotropic conditions. Accordingly, the esterification is conducted in an organic solvent which dissolves the reactants as well as the resultant resin and which is preferably substantially insoluble in water. Examples of these are: benzene, toluene, xylene, chloroform, carbon tertachloride, ethylene dichloride, propylene dichloride, ethylene and propylene trichlorides, butylene dichloride and trichloride and different concentrations of solvent. The range of preferred concentrations for the inert solvent is from about 25% to about 50%. An esterification catalyst is usually necessary because a comparatively low temperature is employed. Examples of these are thymol sulfonic acid, d-camphor sulfonic acid, naphthalene sulfonic acid and p-toluene sulfonic acid. Obviously other known esterification catalysts could be used. A resin having any particular acid number if made azeotropically will usually have a lower viscosity than one of the corresponding acid number not made azeotropically.

PREPARATION OF RESIN "D" 98 parts of maleic anhydride (vacuum distilled), 106 parts of diethylene glycol (vacuum distilled), about 1'75 parts ethylene dichloride and about 3 parts d-camphor sulfonic acid were mixed in a reaction chamber. The heating was conducted in an oil bath maintained at 130145 C. for nine hours. The distillation temperature began at about C. but gradually rose during the heating. The apparatus was so arranged that the water would be separated from the reflux. A light yellow resin with an acid number of about 19.8 was produced after driving off the volatile ingredients including the ethylene dichloride.

Similar results were obtained using thymol sulfonic acid and approximately the same proportiOn-s except that only about 148 parts of ethylene dichloride were used. A resin of acid number 11.3 was obtained.

The resins prepared in the manner illustrated above are merely exemplary of the reactive resins which I contemplate using for reaction with a material containing the CH2=C group in the practice of my invention. Other resins of the same type may be prepared in a similar manner.

Among these resins the following may be employed in place of part or all of those mentioned above: ethylene glycol fumarate, diethylene glycol fumarate, alpha; propylene glycol maleate, polyethylene glycol maleates (e. g., hexaethylene glycol maleate), polymethylene glycol maletates (e. g., decamethylene glycol maleate) octadecandiol fumarate, themaleic esters: of 2,2-dimethyl propenediol-1,3, or 1,3-butanediol, of 1,2-propanediol and of 2-ethyl, 2 butyl butanediol-l,3, glycerol maleate undecylenate, triethylene glycol chlormaleate, triethylene glycol terpene maleate (derived from the interaction of /g mol of terpene and 1 mol of maleic in the presence of excess of terpene).

When a resin is treated with a reactive material containing the CH2=C group, the material may or may not dissolve the resin depending on the chemical nature of both the material and the resin. If the resin be incompatible with this reactive material, chemical interaction of the type described cannot occur in that compatibility has not been established. Under these conditions another solvent may then be introduced as an additional constituent.

If the solvent is inert, it plays no part in the reaction but is so selected that both the reactive material and the resin are soluble yielding a homogeneous system of reactive material, inert solvent and resin. This invention relates to compatible combinations of a reactive resin and a reactive material containing the CH2=C group. Such combinations may be obtained by the use of inert blending solvents where necessary although the use of only reactive materials containing the CH2=C group which act as solvents is preferred.

The terms compatible and homogeneous as used in the specificationand claims are intended to indicate a system, the constitutents of which are uniformly distributed throughout the whole mass, and when applied to solutions, to indicate that these may be either true solutions or colloidal solutions as long as they are substantially stable.

When a reactive resin and a reactive material containing the CH2=C group undergo chemical reaction, certain possibilities arise. The reactive resin and reactive material may combine in such a manner as to lead to the formation of a resinous colloidal entity and the end-product is clear, glass-like and homogeneous. Alternatively, the reactive resin and the reactive material may interact in such a manner as to yield colloidal entities wherein varying degrees of opacity or colloidal colors result. The end-prodnot under these conditions may be partially translucent or opaque. I

The final resin composition is obtained by dissolving a resin containing the alpha. beta enal coma.)

groups in a reactive material containing the group C=CH2. The'chemical reaction which is believed to take place is that the reactive material combines with the resin at the points of unsaturation yielding a less unsaturated system which is essentially insoluble and infusible. Ordinarily when a resin is dissolved in a solvent, the changes which occur are physical in nature. The resin may be isolated from the solvent mixture chemically unchanged. In the present invention, however, the combination of the reactive material containing the CH2=C group which acts as the solvent and reactive resin becomes an inseparable entity, the original ingredients not being removed by the solvents for the original ingredients.

Through the use of a small amount of reactive alkyd resin dissolved in a large amount of reactive material containing the CH2=C group, the final composition contains not only the ester groupings which were originally present in the alkyd resin 'but also the carbon-to-carbon molecular bonds whichlink the reactive material and the reactive resin. Through the use of a small amount of resin and a large amount of reactive material, the composite resin is no longer soluble in those inert solvents wherein the reactive material resinified alone would dissolve. Under long exposure to'the inert solvent, the composite resin will tend to imbibe a certain quantit of inert solvent but it does not possess the solubility of the reactive material when resinified alone. This property is a distinct advantage in that the physical contour of an object made of the polymerized resin is not lost through solution.

Comparison of the softening point of the reactive material containing the CH2=C group alone and of the softening point of the composite resin formed through interaction of the resin and reactive material shows that the soften- .ing point of the latter has been raised. The sofpoint when too high, on the other hand, results v in a composition which will not soften sufliciently in a mold. Roughly three types of compositions exist with respect to the ratio of resin to reactive material containing the CHz=C group. First, a large amount of reactive material and a small amount of resin; second, sub stantial quantities of both ingredients; and third, a large amount of resin and a small amount 01.

' reactive material. Thesecond composition when fully cured possesses no softening point. The

- first and third varieties of composition when cured may, underhigh temperatures and pressure, be made to flow slightly.

The composition obtained from substantial quantities of both reactive material containing the CIE=C group and reactive resin in the cured state may be machined, turned on a lathe, sanded and polished and used in general as a turnery composition. The absence of softening renders the material particularly adaptable to this purpose. In that it is unfiowable, it may be machined without danger of softening and gumming tools. Moreover, such a composition may, if desired, be obtained in large blocks.

My resins may be utilized in: moldings, with or without filler; laminated materials as the bonding agent; adhesives; coating compositions for use in finishes for wood, metals or plastics, or in the treatment of fibrous materials such as paper, cloth or leather; as impregnating agents for fibrous materials; as assistants in dyeing, etc.

In order to use the composition for molding, it may be necessary to prevent the composition from curing too fast. During the change from a liquid to a hard resin, varying stages of hardness exist and by interrupting the reaction at a definite point, the material may then be placed in a form and hardened under heat. Sheets of resin may be twisted, or made to conform to a pattern, and then subsequently cured in the shaped form by heat alone.

One manner in which this may be accomplished is to polymerize the reactive resin and reactive material containing the CH2=C group without catalysts until the material is no longer fluid but still not completely cured. By grinding this partially polymerized material a molding composition is obtained which can then be shaped under heat and pressure.

Example 27 A mixture of about 40 parts by weight of diallyl phthalate and about parts by weight of ethylene glycol maleate resin (acid number 18) was mixed with 0.2% benzoyl peroxide. This would ordinarily gel in five tov six minutes at C. The mixture was prewarmed for two minutes at 90 C. and poured into the mold, the pressure raised to 2000 pounds for about two minutes and then lowered to 1000 pounds. The mold was 21 opened after eight minutes to yield a clear hard disk.

Example 28 A mixture of equal parts by weight of butylene glycol' fumarate, (prepared by heating molar quantities of butylene glycol and Iumaric acid at about 175 C. until the resin has an acid number of about 50) and diallyl phthalate is treated with 0.5% of benzoyl peroxide and poured into a mold,

the sides of which are two sheets of plate glass spaced A; inch apart. The assembly is heated for about V: hour at 100 C. Under these conditions, a flexible sheet is formed.

The sheet may be distorted and bent into various forms. the resin hardens and assumes the form imposed. 1

One procedure isas follows: A mandrel was lightly covered with glycerol, the flexible sheet is bent over the mandrel and the resin is covered with glycerol. A thin sheet of metal is then superimposed on the assembly and secured mechanically. The entire mass is heated in an oven for 1 hour at 150 C. A hardened shaped mass results.

The glycerol is used to maintain the original clear surface. It is particularly useful where one surface is glass since the cured resin may adhere very tenaciously to glass.

All types of simple curves can readily be fashioned. Compound curves are more difficult to produce since the resin in the semi-cured stage may be distensibleto only a limited extent.

To produce moldings or laminated materials combinations of reactive resin and reactive material containing the CH2=C group may be mixed with one or more of the various fillers, e, g., wood flour, wood fiber, paper dust, clay, diatomaceous earths, zein, glass wool, mica. granite By further curing in the bent form dust, silk flock, cotton flock, steel wool, silicon carbide, paper, cloth of any fiber including glass, sand, silica flour, white, black or colored pigments, etc. Such mixtures may be partially polymerized, ground and molded. On the other hand, the liquid composition may be bodied and introduced directly into a mold and polymerization from a viscous liquid to a solid resin conducted in one step.

.In that the composition of reactive resin and reactive material is initially quite limpid, it may be used for impregnating various porous objects or employed as a coating composition.

If the polymerizable compositions are to be molded under low pressure (e. g., 0-50 pounds/ sq. in.) thecomposition may be employed without bodying or partial polymerization.

The liquid polymerizable mixture may be introduced in a positive mold without any filler. In this instance, however, the reaction becomes quite exothermic but this may be conveniently controlled by the addition of a suitable polymerization inhibitor.

The ratio of reactive material containin the CH2=C group to reactive resin in the final composition willnot only have a bearing on the softening point and on methods of working the resin but on various other physical properties, e. g., light transmission, scratch resistance, indentation hardness and are resistance. By a judicious selection of the ratio of reactive material to reactive resin a composition best suited to these varying needs of industry may be fabricated.

The methods by which the reactive material containing the CH2=C group may be made to combine are various. Heat, light or catalysts may be used or combinations of these, or a combination of heat and pressure.

During the transformation of the soft, limpid resinous composition to a hard massive structure, various stages occur which may be roughly separated as follows: first, the induction period wherein the material remains as a sol which slowly increases in viscosity; secondly, the transformation of the sol into a gel; and third, the hardening of the gel. During the transformation of the sol to a gel, an exothermic reaction occurs which may be very violent" if uncontrolled. Moreover, the gel has relatively poor heat conductivity resulting in heat being transferred poorly through the mass, not only external heat but the heat that is generated during chemical reaction. Cognizance has to be taken of these features in the hardening of the composition, particularly in the casting or molding of large blocks.

Light when used alone causes a relatively long induction period and during the transformation of the sol to the gel requires cooling to overcome the exothermic reaction especially when a powerful source of light is used for final curing. Using heat alone, gelation occurs readily enough at appropriate temperatures but since the gel,

when formed, has poor heat conductivity, fracturlng may occur in the last stage. Through the use of heat and catalyst, the reaction may become very violent unless the heating is carefully controlled.

Various combinations of these three factors may be used to bring about hardening of the mass. Mild heating of the reactive resin and reactive material containing the CH2=C group with or without inhibitors brings about a very gradual increase in viscosity which may be controlled quite easily and readily. When the solution has taken on an appropriate consistency, then accelerators may be introduced and heating conducted at a very much lower temperature. Mild heating may first be used and the mass then exposed to light. Use of superoxides and light is very effective. In other words through the use of initial heating or bodying, the induction time maybe decreased markedly.

While I have specifically described the reaction of mixtures of a reactive resin and a reactive material containing the CH2=C group in the liquid state I am not precluded from reacting the reactive material in the vapor state with the resin. Compositions containing a reactive resin and a reactive material containing the CH2=C group are originally liquid compositions and by proper treatment at relatively low temperature they can be converted into hard masses. The wide divergence of the properties of such compositions enables them to be used in a variety of difierent ways. In the liquid form they may be used as an adhesive, impregnating agent or as a surface coating. In that the hardening does not depend upon evaporation, the liquid may be applied to the surfaces desired with the reactive resin mixed with the reactive material containing the CH2=C group which acts as the solvent and combining in situ to form a homogeneous adhesive. Such an adhesive can be used for bringing diverse substances together, wood metal, glass,

rubber, or otherresinous compositions such as phenolic or urea condensation products. As a surface composition in the liquid form, softening agents, cellulose ethers or esters couldbe added as well as natural or artificial resins, and the hardeningbrought about through catalysts such as cobalt salts, oxygen liberating substances or hardening could be accomplished with light. Since these compositions dry from the bottom rather than from the top, the latter frequently remains tacky for a relativelylengthy period. In order to overcome this, drying oil fatty acids, e. g., linseed oil fatty acids are added to the esterification mixture in making the original reactive resin and this will cause the top surface to dry quickly upon subsequent polymerization with a reactive material containing the CH2==C group. In this way a coating composition is obtained which dries both from top and bottom.

The liquid resinous composition, moreover, may be cast or molded and after hardening may be isolated as a finished product, or could be cut, turned and polished into the desired finished product. Provided the surface of the mold is highly polished, the resinous substance would acquire a clear, smooth finish from the mold. The compositions so obtained being insoluble are not easily attacked by solvents and being infusible may be worked with ordinary wood working or metal tools. The artificial mass can be cut, turned on a lathe, polished and sanded without superficial softening and streaking.

Obviously natural resins or other synthetic resins may be admixed with the resins of this invention in order to obtain products suitable for particular purposes. Examples of these are shellac, cellulose esters and ethers, urea resins, phenolic resins, alkyd resins, ester gum, etc. The resins of my invention may also be mixed with rubber or synthetic rubber-like products if desired.

In that many of these resins are originally transparent and free of color, they may be colored with suitable dyes to a wide variety of transparent soft pastel shades. An example of a suitable dye is Sudan IV. Darker shades may be obtained, if desired, e. g., with nigrosine.

It may be desirable in some instances to form a copolymer of one or more substances containing the group CH2=C and at least one polymerizable unsaturated alkyd resin and, after molding or casting this into any desired shape, to apply a coating of a harder copolymer to the outside, thus obtaining the same effect as is obtained in the metallurgical fields by case hardening. Similarly, inserts may be filled with a hard resin in order to act as bearing surfaces or for some other purpose. Such coatings or inserts adhere tenaciously and appear to become integral with the original piece. In order to secure the best results in manufacturing such products, it is desirable to first abrade the surface of the article before the application of the harder film. During the curing operation, the abrasion marks disappear. This treatment is also of considerable importance since it may also be used to refinish articles which might have been marred in use.

Many of the advantageous properties of the resin resulting from the polymerization of mixturescontaining reactive materials containing the CH2=C group and reactive resins are apparent from the foregoing disclosure. Several important advantages are now to be set forth.

In molding and casting operations curing takes place either in the presence or absence of air very rapidly. This is of great importance in curing large blocks. Other alkyd resins require a very much longer time to cure in large blocks, 1. e., many months, whereas the composition of frequently contain a. reactive resin and reactive materials containing the CHa=C group require only a few days, at the most.

Another important advantage is the fact that the-reactive material containing the CH2=C group which acts as the solvent combines with the resin leaving no residual solvent and giving no problems as to solvent removal.

One of the outstanding advantages of these resinsis quick curing time which renders them available for injection molding, blow molding, and extrusion moi g.

Castings which are polymers of such substances as methyl methacrylate, for example, ubbles which are formed in the lower part of t e casting. Inasmuch as the present invention is directed to systems wherein the polymerization proceeds from the bottom to the top, no bubbles are trapped in the casting.

Similar advantages are present in coating operations suchas the lack of shrinkage of the film due to loss of solvent because of the combination between the reactive resin and the reactive material containing the CH==C group which acts as the solvent. tion dries from the bottom, there are no bubbles from the solvent and there is no water driven off. A clear bubble-free, impervious coating is, therefore, more readily obtainable with the combinations of a reactive resin and reactive material containing the CH2=C group than with other coating compositions, Since there is no solvent to be removed and since air is not needed to dry the compositions, relatively thick layers may be applied in one operation. I

This application is a continuation-in-part of my copending applications Serial Nos. 248,536, filed December 30, 1938, now abandoned, 349,240, filed August 1, 1940, now abandoned, and 487,034, filed May 14, 1943.

Obviously many other reactants and modifications may be used in the processes outlined in alpha, beta unsaturated polycarboxylie acid.

3. A polymer of a homogeneous mixture including diallyl phthalate and a polymerizable unsaturated alkyd resin obtained by the esterification of a mixture including diethylene glycol and fumaric acid.

4. A composition comprising the product of polymerization of, a polymerizable mixture containing diallyl phthalate and an unsaturated alkyd resin which is copolymerizable therewith.

' 5. Asa new product, a resinous interpolymer obtained by interpolymerization of a mixture of copolymerizable materials consisting of diallyl phthalate and diethylene glycol maleate.

6. The method of producing an insoluble and infusible resinous composition which comprises heating a mixture of diethylene glycol maleate, diallyl phthalate and. a small amount of an organic peroxide as a poymerization catalyst and Furthermore, the composi- 25 continuing said heating until an insoluble, infusible resin results.

7. As a new product, a resinous interpolymer obtained by interpolymerization' of a mixture of copolymerizable materials consisting of diallyl phthalate and an unsaturated alkyd resin.

8. As a new product, a resinous interpclymer obtained by interpolymerization of a mixture of copolymerizable materials consisting of diallyl phthalate and diethylene glycol fumarate.

9. A process which. comprises polymerizing a homogeneous mixture of (1) diallyl phthalate (2) an unsaturated alkyd resin and (3) a catalyst for accelerating the copolymerization of (1) and 10. A polymerizable composition comprising (1) a pclymerizabl'e' unsaturated alkyd resin, (2) diallyl phthalate and (3) a catalyst for accelerating the copolymerization of the materials of (1) and (2).

11. A composition comprising the product of polymerization of a polymerizable mixture including (1) diallyl phthalate and (2) an unsaturated alkyd resin obtained by reaction of ingredients comprising a dihydric alcohol and an alpha unsaturated alpha beta dicarboxylic acid, said materials of (1) and (2) being copolymerizable and compatible.

(2) diallyl phthalate.

continuing said heating until an insoluble, infusible resin results.

14. A polymerizable composition comprising (1) a polymerizable unsaturated alkyd resin and EDWARD L. KROPA.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name I Date 2,005,414 Dykstra June 18, 1935 2,155,590 Garvey Apr. 1939 2,195,362 Ellis Mar, 26, 1940 

